Arun Bhujel, Salma Akter, Muhammad Qasim Ali and G. Barratt Park
{"title":"三氟碘甲烷中 ν3-ν6 科里奥利相互作用的再研究","authors":"Arun Bhujel, Salma Akter, Muhammad Qasim Ali and G. Barratt Park","doi":"10.1039/D4CP02640C","DOIUrl":null,"url":null,"abstract":"<p >The lowest-frequency fundamental <em>ν</em><small><sub>6</sub></small> of trifluoroiodomethane (CF<small><sub>3</sub></small>I) has never been directly observed and analyzed at high resolution in the gas phase. The <em>ν</em><small><sub>6</sub></small>(e) level interacts with <em>ν</em><small><sub>3</sub></small>(a<small><sub>1</sub></small>) at 286.297 cm<small><sup>−1</sup></small><em>via</em> a <em>b</em>-axis Coriolis interaction, which perturbs the rotational structure of both levels. In this work, we report low-<em>J</em> microwave transitions (for <em>J</em> ranging from 0–2) within the <em>ν</em><small><sub>6</sub></small> vibrational level. The <em>l</em>-type doubling observed in our spectrum agreed poorly with the predictions of previously published models of the interacting <em>ν</em><small><sub>3</sub></small>–<em>ν</em><small><sub>6</sub></small> levels, prompting us to refine the model. We performed <em>ab initio</em> anharmonic force-field calculations, which were used to constrain some of the parameters, and which served as a check on some of the floated parameters. We fit a dataset consisting of 3593 transitions, which combined our measurements with previous microwave, millimeter wave, and high-resolution infrared observations. A reasonable set of fit parameters is obtained with <em>ν</em><small><sub>6</sub></small> = 267.28 cm<small><sup>−1</sup></small>, but we cannot rule out a lower value of <em>ν</em><small><sub>6</sub></small> = 261.5 cm<small><sup>−1</sup></small> consistent with analyses of the vibrational level structure.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 44","pages":" 27902-27911"},"PeriodicalIF":2.9000,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Reinvestigation of the ν3–ν6 Coriolis interaction in trifluoroiodomethane†\",\"authors\":\"Arun Bhujel, Salma Akter, Muhammad Qasim Ali and G. Barratt Park\",\"doi\":\"10.1039/D4CP02640C\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The lowest-frequency fundamental <em>ν</em><small><sub>6</sub></small> of trifluoroiodomethane (CF<small><sub>3</sub></small>I) has never been directly observed and analyzed at high resolution in the gas phase. The <em>ν</em><small><sub>6</sub></small>(e) level interacts with <em>ν</em><small><sub>3</sub></small>(a<small><sub>1</sub></small>) at 286.297 cm<small><sup>−1</sup></small><em>via</em> a <em>b</em>-axis Coriolis interaction, which perturbs the rotational structure of both levels. In this work, we report low-<em>J</em> microwave transitions (for <em>J</em> ranging from 0–2) within the <em>ν</em><small><sub>6</sub></small> vibrational level. The <em>l</em>-type doubling observed in our spectrum agreed poorly with the predictions of previously published models of the interacting <em>ν</em><small><sub>3</sub></small>–<em>ν</em><small><sub>6</sub></small> levels, prompting us to refine the model. We performed <em>ab initio</em> anharmonic force-field calculations, which were used to constrain some of the parameters, and which served as a check on some of the floated parameters. We fit a dataset consisting of 3593 transitions, which combined our measurements with previous microwave, millimeter wave, and high-resolution infrared observations. A reasonable set of fit parameters is obtained with <em>ν</em><small><sub>6</sub></small> = 267.28 cm<small><sup>−1</sup></small>, but we cannot rule out a lower value of <em>ν</em><small><sub>6</sub></small> = 261.5 cm<small><sup>−1</sup></small> consistent with analyses of the vibrational level structure.</p>\",\"PeriodicalId\":99,\"journal\":{\"name\":\"Physical Chemistry Chemical Physics\",\"volume\":\" 44\",\"pages\":\" 27902-27911\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-10-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Physical Chemistry Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/cp/d4cp02640c\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/cp/d4cp02640c","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Reinvestigation of the ν3–ν6 Coriolis interaction in trifluoroiodomethane†
The lowest-frequency fundamental ν6 of trifluoroiodomethane (CF3I) has never been directly observed and analyzed at high resolution in the gas phase. The ν6(e) level interacts with ν3(a1) at 286.297 cm−1via a b-axis Coriolis interaction, which perturbs the rotational structure of both levels. In this work, we report low-J microwave transitions (for J ranging from 0–2) within the ν6 vibrational level. The l-type doubling observed in our spectrum agreed poorly with the predictions of previously published models of the interacting ν3–ν6 levels, prompting us to refine the model. We performed ab initio anharmonic force-field calculations, which were used to constrain some of the parameters, and which served as a check on some of the floated parameters. We fit a dataset consisting of 3593 transitions, which combined our measurements with previous microwave, millimeter wave, and high-resolution infrared observations. A reasonable set of fit parameters is obtained with ν6 = 267.28 cm−1, but we cannot rule out a lower value of ν6 = 261.5 cm−1 consistent with analyses of the vibrational level structure.
期刊介绍:
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.